Organomanganese indole compounds and process for preparing same



United States Patent 3,321,485 ORGANOMANGANESE INDQLE COMPOUNDS ANDPROCESS FOR PREPARING SAME John Kozikowski, Walled Lake, Mich, andMichael Cais,

Haifa, Israel, assignors to Ethyl Corporation, New York, N .Y., acorporation of Virginia No Drawing. Original application Dec. 28, 1960.Ser. No. 78,820. Divided and this application May 3, 1965, Ser. No.463,426

2 Claims. (Cl. 260-319.1)

This application is a division of application Ser. No. 78,820, filedDec. 28, 1960.

This invention relates to a variety of organometallic compounds and theprocesses employed in their production. More specifically, thisinvention relates to compounds and processes involving the use of anacylcyclopentadienyl manganese tricarbonyl compound.

An object of our invention is to provide new organometallic compoundsand processes for their preparation. A further object is to provideacylcyclopentadienyl manganese tricarbonyl derivatives and processes fortheir preparation. from a reading of the specification and claims whichfollow.

When an acylcyclopentadienyl manganese tricarbonyl is reacted with ahydrazine compound having the formula:

in which Z is a hydrocarbon group containing from one to about 18 carbonatoms which can be an aryl, an alkyl, or a cycloalkyl group, a hydrazonederivative of acylcyclpoentadienyl manganese tricarbonyl is obtained. Apreferred form is the reaction of acetylcyclopentadienyl manganesetricarbonyl with phenyl hydrazine to form the phenyl hydrazonederivative of acetylcyclopentadienyl manganese tricarbonyl. The objectsof this invention are accomplished by preparing an indole derivative ofcyclopentadienyl manganese tricarbonyl from a phenyl hydrazonederivative of acylcyclopentadienyl manganese tricarbonyl. The reactionis generally carried out in the presence of a neutral solvent by heatingthe reaction mixture at reflux for a short period of time at atemperature of about 100 C. To further illustrate this form of ourinvention, there is presented the following example.

Example I A solution comprising grams of acetylcyclopentadienylmanganese tricarbonyl dissolved in 50 ml. of ethanol was heated with 2.1grams of phenyl hydrazine on a steam bath for minutes. The reactionmixture was then cooled and diluted with 3 ml. of water and filtered toyield 6.3 grams of yellow crystals which were the phenyl hydrazonederivative of acetylcyclopentadienyl manganese tricarbonyl. The crystalshad a melting point of IDS-107 C. On further dilution of the filtratewith water, there were obtained an additional 0.4 gram of the phenylhydrazone derivative having a melting point of 104-106 C. The totalyield of product was 98.5 percent.

The phenyl hydrazone derivative of acetylcyclopentadienyl manganesetriearbonyl can then be treated with a Lewis acid catalyst in thepresence of concentrated hydrochloric acid to yield the indolederivative of cyclopentadienyl manganese tricarbonyl. A preferred Lewisacid catalyst for this reaction is zinc chloride. To further illustratethis aspect of our invention, there is presented the following example.

Example II Acetylcyclopentadienyl manganese tricarbonyl phenyl hydrazone(4 grams) and zinc chloride (20 grams) were Additional objects willbecome apparentv heated on an oil bath at C. The temperature was raisedto 170 C. over a 30-minute period while stirring the mixture. Themixture was kept at 170 C. for 10 minutes after which 20 grams of sandwere added and mixed into the original mixture. After cooling, themixture was diluted with water (100 ml.) and concentrated hydrochloricacid (3 ml.) and heated on the steam bath for 1 /2 hours.

The cooled mixture was filtered and the residue was boiled with ethanol(100 ml.) and Norit-A. The mixture was filtered through Celite; theCelite was washed with hot ethanol and the filtrate and washings werecombined and evaporated on a steam bath. The residue was trituratedseveral times with a boiling mixture of benzenepetroleum ether (1:1volume ratio), and the organic solvents were collected, filtered, andconcentrated to a small volume. 0n cooling, there were obtained twograms of yellow crystals having a melting point of 132-134 C. Thefiltrate afiorded another 0.9 gram of crystals on cooling. An analyticalsample was crystallized from benzene-petroleum ether and had a meltingpoint of l35l36 C.

Calculated for c H NMnO z C, 60.1; H, 3.13; N, 4.30; Mn, 17.2. Found: C,60.5; H, 3.40; N, 3.95; Mn, 17.3.

The preparation of other acylcyclopentadienyl manganese tricarbonylcompounds is described in our copending patent application Ser. No.78,820, filed Dec. 28, 1960.

Among the important uses of our compounds is their use as fuel and oiladditives. For example, they are useful antiknocks when added togasoline. They may be used as primary antiknocks in which they are themajor antiknock component in the fuel or as supplemental antiknocks.When used as supplemental antiknocks, they are present as the minorantiknock component in the fuel in addition to a primary antiknock suchas a tetraalkyllead compound. Typical alkyllead compounds aretetraethyllead tetrabutyllead, tetramethyllead and various mixed leadalkyls such as dimethyldiethyllead, diethyldibutyllead and the like.When used as either a supplemental or primary antiknock, our compoundsmay be present in the gasoline in combinaton with typical scavengerssuch as ethylene dichloride, ethylene dibromide, tricresylphosphate,trimethylphosphate and the like.

The compounds of our invention have further utility as additives toresidual and distillate fuels generally, e.g., jet fuels, home heaterfuels and diesel fuels, to reduce smoke and/ or soot formation. Also,they may be employed as additives to lubricating oils in which case theyact to improve the lubricity of the base oil. In addition, they may beemployed as additives to solid fuels to control burning rate.

Our compounds are further useful in many metal plating applications. Inorder to effect metal plating using the compounds, they are decomposedin an evacuated space containing the object to be plated. Ondecomposition, they lay down a film of metal on the object. The gaseousplating may be carried out in the presence of an inert gas so as toprevent oxidation of the plating metal or the object to be plated duringthe plating operations.

The gaseous plating technique described above finds wide application informing coatings which are not only decorative but also protect theunderlying substrate material.

Deposition of metal on a glass cloth illustrate the applied process. Aglass cloth band weighing one gram is dried for one hour in an oven atC. It is then placed in a tube which is devoid of air and there is addedto the tube 0.5 gram of bromoacetylcyclopentadienyl manganesetricarbonyl. The tube is heated at 400 C. for one hour after which timeit is cooled and opened. The cloth has a uniform metallic grayappearance and exhibits a gain in weight of about 0.02 gram.

A further utility for our compounds is as drying agents in which casethe compounds are incorporated in paints, varnish, printing inks,synthetic resins of the drying oil type, oil enamels and the like. Astill further utility for our compounds is their use as chemicalintermediates in preparation of metal-containing polymeric materials orin the preparation of new organic materials.

Having fully defined the novel compounds of our invention, their mode ofpreparation and their many utilities, we desire to be limited onlywithin the lawful scope of the appended claims.

We claim:

1. [(2 indolyl)cyclopentadienyl]manganese tricarbonyl.

2. Process comprising reacting the phenyl hydrazone derivative ofacetylcyclopentadienyl manganese tricarbonyl with zinc chloride catalystin the presence of concentrated hydrochloric acid to yield[(2-indolyl)cyclopentaclienyhmanganese tricarbonyl.

References Cited by the Examiner Elderfield, Heterocyclic Compounds,vol. 3, Wiley, 1952, pp. 8-11 relied upon.

Fieser et al., Advanced Organic Chemistry, Reinhold, 1961, p. 492 reliedon.

ALEX MAZEL, Primary Examiner.

HENRY R. JILES, Examiner.

DONALD G. DAUS, Assistant Examiner.

1. ((2 - INDOLYL)CYCLOPENTADIENYL)MANGANESE TRICARBONYL.